KR102376913B1 - Hyperbranched polymers, metal recovery agents, metal recovery methods and catalyst activity inhibitors - Google Patents

Abstract

It is represented by the following formula (1) and provides a hyperbranched polymer having a weight average molecular weight of 1,000 to 1,000,000. In Formula (1), A ¹ is a group containing an aromatic ring, A ² is a group containing an amide group, A ³ is a group containing sulfur, R ⁰ is hydrogen or C 1-10 substituted or unsubstituted hydrocarbon group, m1 is 0.5-11, and n1 is 5-100.
[Formula 1]

Description

Hyperbranched polymers, metal recovery agents, metal recovery methods and catalyst activity inhibitors

The present invention relates to a novel hyperbranched polymer, and also to a metal recovery agent, a metal recovery method, and a catalyst activity inhibitor using the hyperbranched polymer.

Hyperbranched polymers are classified as dendritic polymers along with dendrimers. The dendritic polymer is a polymer composed of a molecular structure that frequently repeats regular branching. A dendrimer is a spherical polymer with a diameter of several nanometers having a structure in which the dendritic branch is regularly and completely branched around a molecule that becomes a nucleus, and a hyperbranched polymer is different from a dendrimer having a complete dendrimer structure. It is a polymer with different, incomplete aqueous branching. Among dendritic polymers, hyperbranched polymers are advantageous in industrial production because they are relatively easy to synthesize and are inexpensive. As a hyperbranched polymer and its manufacturing method, the hyperbranched polymer of the structure disclosed by patent documents 1 - 3, and its manufacturing method are known, for example.

Japanese Patent No. 5499477 Publication Japanese Patent No. 5748076 Publication Japanese Patent No. 5534244 Publication

The hyperbranched polymer has many terminal groups due to its special branching structure, and expression of various properties is expected depending on the type of the terminal group. The present invention provides a novel hyperbranched polymer that has high metal trapping ability and can be used as a metal recovery agent or catalyst activity inhibitor.

According to the first aspect of the present invention, a hyperbranched polymer represented by the following formula (1) and having a weight average molecular weight of 1,000 to 1,000,000 is provided.

In Formula (1), A ¹ is a group containing an aromatic ring, A ² is a group containing an amide group, A ³ is a group containing sulfur, R ⁰ is hydrogen or C 1-10 substituted or unsubstituted hydrocarbon group, m1 is 0.5-11, and n1 is 5-100.

In the formula (1), A ¹ is a group represented by the following formula (2), and A ³ may be a dithiocarbamate group. Moreover, in said Formula ( ¹ ), A2 may also contribute represented by following formula (3).

In formula (3), R ¹ is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms or a single bond, and R ² and R ³ are each a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. or hydrogen.

In the formula (3), R ¹ may be a single bond, R ² may be hydrogen, and R ³ may be an isopropyl group.

In said Formula (1), ^A3 may also contribute represented by following formula (4).

In Formula (4), R< ⁴ > and R< ⁵ > are respectively a C1-C5 substituted or unsubstituted alkyl group, or hydrogen.

In formula (4), R ⁴ and R ⁵ may be an ethyl group.

In Formula (1), 0.5 or more and less than 1.5 may be sufficient as the ratio of the total number of moles of the amide group contained in A2 with respect to the number ^of moles of ^A3 of group containing sulfur. Moreover, 0.5-1.5 may be sufficient as ^A3 is a dithiocarbamate group, and the ratio of the total number of moles ^of the amide group contained in A2 with respect to the number of moles of ^A3 which is group containing sulfur.

In Formula (1), R ⁰ may be a vinyl group. Further, the hyperbranched polymer may be a mixture of a hyperbranched polymer in which R ⁰ is a vinyl group in the formula (1) and a hyperbranched polymer in which R ⁰ is an ethyl group.

According to a second aspect of the present invention, there is provided a metal recovery agent for recovering the metal in a liquid in which the metal is dissolved, comprising the hyperbranched polymer of the first aspect.

According to a third aspect of the present invention, as a metal recovery method for recovering the metal in a liquid in which the metal is dissolved, the hyperbranched polymer of the first aspect is dissolved in a solvent to prepare a hyperbranched polymer solution; There is provided a metal recovery method comprising applying a branched polymer solution on a substrate to form a hyperbranched polymer layer, and contacting the liquid with the hyperbranched polymer layer to adsorb and recover the metal in the liquid.

According to a fourth aspect of the present invention, there is provided a catalytic activity inhibitor for inhibiting the catalytic activity of an electroless plating catalyst, comprising the hyperbranched polymer of the first aspect.

The present invention provides a novel hyperbranched polymer that has high metal trapping ability and can be used as a metal recovery agent or catalyst activity inhibitor.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the hyperbranched polymer of embodiment.
FIG. 2 is an IR spectrum of hyperbranched polymer A1 synthesized in Example 1. FIG.
3 is a ¹ H-NMR spectrum of hyperbranched polymer A1 synthesized in Example 1. FIG.

The hyperbranched polymer of this embodiment is represented by following formula (1).

In formula (1), A ¹ is a group containing an aromatic ring, A ² is a group containing an amide group, A ³ is a group containing sulfur, and R ⁰ is hydrogen or a substitution having 1 to 10 carbon atoms. or an unsubstituted hydrocarbon group, m1 is 0.5-11, and n1 is 5-100.

As long as it is group containing an aromatic ring, although A< ¹ > can use arbitrary things, for example, it is preferable that it is group represented by following formula (2).

When A ¹ is a group represented by Formula (2), the hyperbranched structure of the hyperbranched polymer of the present embodiment has a styrene skeleton. When the hyperbranched structure has a styrene skeleton, it is expected that the weather resistance and heat resistance of the hyperbranched polymer will be improved.

The hyperbranched polymer of the present embodiment has a plurality of terminal groups. In the terminal group of the hyperbranched polymer represented by Formula (1), A ² is a group containing an amide group, and A ³ is a group containing sulfur. In addition, m1 is an average value of the number (repetition number) m ^of the group (A2) containing an amide group in each terminal group. Therefore, m1 does not need to be an integer. The hyperbranched polymer of the present embodiment may have an average value of m1 of 0.5 to 11, and may have a terminal group (m=0) having no group (A ² ) including an amide group.

Below, the repetition number m of the group (A2) containing m1 in said Formula ( ¹ ) and the amide group in each terminal group is demonstrated further. Hyperbranched polymers 100A to 100D schematically shown in Fig. 1 are examples of hyperbranched polymers having a central portion S other than terminal groups and 10 terminal groups. The terminal group E1 indicated by the white circle does not have a group containing an amide group (A ² ) (m=0), and the terminal group E2 indicated by the black circle has one group containing an amide group (A ² ) (m=1), the terminal group E3 shown by the vertical diagonal circle has two groups (A2) containing an amide group (m= ² ). As in the hyperbranched polymers 100A and 100B, a terminal group E1 having no group (A ² ) containing an amide group may be present. In addition, as in the hyperbranched polymer 100C, in all the terminal groups, the number of groups (A ² ) containing an amide group may be the same, and as in the hyperbranched polymer 100A, 100B and 100D, the amide group in each terminal group is included. The number of groups (A ² ) to do does not need to be the same. The number (repetition number) m ^of the group (A2) containing an amide group in each terminal group is 0-11, for example. m1 in Formula (1) is the quotient obtained by dividing the total number of groups (A ² ) containing amide groups in the molecule (the sum of m in the molecule) by the number of terminal groups. In the hyperbranched polymers 100A and 100B, m1 is 0.5, in the hyperbranched polymer 100C, m1 is 1.0, and in the hyperbranched polymer 100D, m1 is 1.5. The value of m1 can be quantified by the same method as NMR method or elemental analysis method.

The hyperbranched polymer of the present embodiment is expected to exhibit various functions by having a plurality of terminal groups. For example, since the terminal group of the hyperbranched polymer represented by said Formula (1) has an amide group and group containing sulfur, it interacts with a metal ion. The hyperbranched polymer of the present embodiment having a plurality of such terminal groups acts as a polydentate ligand of a metal ion and chelates with the metal ion. Thereby, the hyperbranched polymer of this embodiment can adsorb|suck (trap) a metal. By applying this function, the hyperbranched polymer of the present embodiment can be used as, for example, a metal recovery agent or a catalytic activity inhibitor that hinders the catalytic activity of the electroless plating catalyst.

In the formula (1), A ² is not particularly limited as long as it is a group containing an amide group, and the amide group contained in A ² may be any of a primary amide group, a secondary amide group, and a tertiary amide group. do. In addition, A ² may be a contribution containing one amide group, and may be a contribution containing two or more. It is preferable that A2 is group represented by following formula ( ³ ). When A2 is group represented by following formula ( ³ ), the hyperbranched polymer of this embodiment improves a metal capture|acquisition ability, for example.

In formula (3), R ¹ is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms or a single bond, and R ² and R ³ are each a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. or hydrogen. Moreover, in Formula (3), it is preferable that it is preferable that R< ¹ > is a single bond, it is preferable that R< ² > is hydrogen, and it is preferable that R< ³ > is an isopropyl group.

In the formula (1), A ³ is not particularly limited as long as it is a group containing sulfur, and examples thereof include a dithiocarbamate group, a trithiocarbonate group, a sulfide group, and a thiocyanate group, Especially, it is preferable that it is a dithiocarbamate group. When A ³ is a dithiocarbamate group, the hyperbranched polymer of the present embodiment can be easily synthesized, and the metal trapping ability is improved. Moreover, it is preferable that ^A3 is group represented by following formula (4).

In Formula (4), R< ⁴ > and R< ⁵ > are respectively a C1-C5 substituted or unsubstituted alkyl group, or hydrogen. Moreover, in Formula (4), it is preferable that R< ⁴ > and R< ⁵ > are an ethyl group.

The hyperbranched polymer of the present embodiment is expected to exhibit various functions by increasing or decreasing the number of amide groups contained in the terminal groups. The number of amide groups contained in the terminal groups is the molar ratio of the amide groups contained in A ² to the sulfur-containing group A ³ in the hyperbranched polymer represented by Formula (1) (hereinafter, appropriately “molar ratio ( N/S)"). That is, the molar ratio (N/S) is, in the hyperbranched polymer represented by Formula (1), the total number of moles (total number) of amide groups contained in A ² with respect to the number of moles (number) of A ³ , which is a group containing sulfur. ) is the ratio of In addition, in Formula (1), when the number of the amide groups contained in one unit of A ² is one, molar ratio (N/S) is substantially equivalent to the value of m1. Incidentally, the molar ratio (N/S) is, for example, in the ¹ H-NMR spectrum of the hyperbranched polymer (analysis result of ¹ H-nuclear magnetic resonance measurement), A ³ and A ² of a group containing sulfur It can be converted from the ratio of the proton area strength with the amide group contained.

In the hyperbranched polymer of this embodiment, the molar ratio (N/S) may be 0.5-11. The molar ratio (N/S) is within the above range, and the hyperbranched polymer represented by Formula (1) is soluble in tetrahydrofuran (THF), methyl ethyl ketone (MEK), etc., which are general-purpose solvents. Further, by appropriately setting the molar ratio (N/S), the solubility in a lower alcohol having 5 or less carbon atoms can be controlled, for example.

The molar ratio (N/S) may be 0.5 or more and less than 1.5. When the molar ratio (N/S) is within the above range, the solubility of the hyperbranched polymer represented by Formula (1) in a solvent having relatively low polarity, such as cyclohexanone and toluene, is improved. Although the reason for this is not certain, it is estimated that the polarity of a hyperbranched polymer falls by making the number of amide groups contained in a terminal group less than 1.5.

The hyperbranched polymer may be used in the form of a hyperbranched polymer layer on the substrate by first preparing a hyperbranched polymer solution, then applying the hyperbranched polymer solution on a substrate to form a hyperbranched polymer layer. The hyperbranched polymer solution has a low viscosity even at a high concentration. For this reason, even if it apply|coats to the base material of complex shape, the application layer (hyperbranched polymer layer) of a uniform film thickness can be formed. In addition, even if the hyperbranched polymer layer is a thin film, since it contains many terminal groups, sufficient properties can be exhibited. The solvent of the hyperbranched polymer solution needs to be appropriately selected according to the type of the substrate.

In the hyperbranched polymer of the present embodiment, the molar ratio (N/S) may be 0.5 to 3.5, preferably 0.5 to 2.5. The hyperbranched polymer represented by Formula (1) as molar ratio (N/S) is in the said range improves metal trapping ability. Although the reason for this is not certain, when the molar ratio (N/S) is smaller than this range, the number of amide groups interacting with the metal in the terminal groups of the hyperbranched polymer represented by the above formula (1) is insufficient, and the molar ratio When (N/S) is larger than this range, the terminal group becomes long and the amide group interacting with the metal becomes excessive, so that a steric modification occurs in the chelate structure formed from the terminal group and the metal. As a result, the chelate bond This is presumed to be due to destabilization.

Moreover, in the hyperbranched polymer of this embodiment represented by said Formula (1), it is preferable that ^A3 is a dithiocarbamate group, and it is preferable that molar ratio (N/S) is 0.5-1.5. When A ³ is a dithiocarbamate group, the terminal group of the hyperbranched polymer represented by the formula (1) is relatively short, and a hyperbranched polymer having a structure having a relatively small molar ratio (N/S) can be efficiently synthesized. A ³ in the formula (1) is a dithiocarbamate group, and the hyperbranched polymer having a molar ratio (N/S) of 0.5 to 1.5 has a high metal trapping ability.

In the formula (1), any hydrocarbon group can be used as R ⁰ as long as it is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group may be a chain or cyclic saturated aliphatic hydrocarbon group, a chain or cyclic unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group. When R ⁰ is a substituted hydrocarbon group, the substituent is, for example, an alkyl group, a cycloalkyl group, a vinyl group, an allyl group, an aryl group, an alkoxy group, a halogen group, a hydroxyl group, an amino group, an imino group, a nitro group, a silyl group, or An ester group, etc. may be sufficient. In addition, an unsubstituted hydrocarbon group may be sufficient as R ^<0> , for example, a vinyl group or an ethyl group may be sufficient as it.

The hyperbranched polymer of the present embodiment may be a mixture of hyperbranched polymers having different R ⁰ in Formula (1). For example, when R ⁰ has an unsaturated bond, in the synthesis process of the hyperbranched polymer, some addition reaction may occur to a part of the unsaturated bond to form a saturated bond. In this case, in the formula (1), a mixture of a hyperbranched polymer in which R ⁰ is an unsaturated hydrocarbon group and a hyperbranched polymer in which R ⁰ is a saturated hydrocarbon group is obtained. The hyperbranched polymer of the present embodiment may be a mixture of a hyperbranched polymer in which R ⁰ is a vinyl group in the formula (1) and a hyperbranched polymer in which R ⁰ is an ethyl group.

The weight average molecular weight of the hyperbranched polymer of this embodiment is 1,000-1,000,000. Further, the hyperbranched polymer of the present embodiment has a number average molecular weight of 3,000 to 30,000, preferably a weight average molecular weight of 10,000 to 300,000, a number average molecular weight of 5,000 to 30,000, and a weight average molecular weight of 14,000 It is more preferable that it is ~200,000. When the number average molecular weight or the weight average molecular weight is smaller than the above range, the hyperbranched polymer may be dissolved in water. On the other hand, when the number average molecular weight or the weight average molecular weight is larger than the above range, the solubility of the hyperbranched polymer in a solvent is lowered, and there is a fear that the use as a metal recovery agent or catalyst activity inhibitor may become difficult. In addition, the weight average molecular weight and number average molecular weight of a hyperbranched polymer are measured by polystyrene conversion by gel permeation chromatography (GPC), for example.

The method for synthesizing the hyperbranched polymer of the present embodiment is not particularly limited, and may be synthesized by any method. For example, the hyperbranched polymer of the present embodiment may be synthesized using a commercially available hyperbranched polymer as a starting material. Further, the hyperbranched polymer of the present embodiment may be synthesized by sequentially performing monomer synthesis, monomer polymerization, terminal group modification, and the like. In addition, the weight average molecular weight and number average molecular weight of the hyperbranched polymer of this embodiment, and m1 and n1 in Formula (1) are within a predetermined range by adjusting the ratio of reagents used for synthesis, synthesis conditions, etc. by any method. Can be adjusted.

The use of the hyperbranched polymer of this embodiment is not specifically limited. For example, metal trapping agent, polyfunctional crosslinking agent, metal or metal oxide dispersant or coating agent, paint, ink, adhesive, resin filler, various molding materials, nanometer-sized pore former, chemical mechanical abrasive agent, functional substance It is suitably used as a carrier material, a nanocapsule, a photonic crystal, a resist material, an optical material, an electronic material, an information recording material, a printing material, a battery material, a medical material, a magnetic material, an intermediate raw material, etc.

In particular, the hyperbranched polymer of the present embodiment can be used as a metal recovery agent for recovering a metal in a liquid in which the metal is dissolved by utilizing the property of trapping the metal. For example, you may implement the following metal recovery methods. First, a hyperbranched polymer is dissolved in a solvent to prepare a hyperbranched polymer solution, and then, the hyperbranched polymer solution is applied on a substrate to form a hyperbranched polymer layer. Then, the liquid in which the metal is dissolved is brought into contact with the hyperbranched polymer layer to adsorb and recover the metal (metal ion). When a porous body or fiber having a large surface area is selected as the substrate, the contact area between the liquid in which the metal is dissolved and the metal recovery agent (hyperbranched polymer) is increased, and the metal recovery efficiency is improved. The liquid and metal in which the metal is dissolved are not particularly limited. Examples of the liquid in which the metal is dissolved include seawater, waste liquid, sludge, and sewage, and examples of the metal include noble metals such as Pd, Pt, Ag, Au, Co, Ti, Nb, V , rare earth elements, and the like. Metals recovered by adsorption to the hyperbranched polymer layer are, for example, noble metals, etc., and in the case of reuse, the hyperbranched polymer layer to which the metal has been adsorbed is removed by burning, etc. for each substrate to remove the metal. You can do it. In addition, when the recovered metal is a hazardous metal, the hyperbranched polymer layer to which the metal is adsorbed may be discarded for each substrate.

Moreover, similarly to the metal recovery agent, using the property of trapping metals, the hyperbranched polymer of the present embodiment can be used as a catalytic activity inhibitor that prevents the catalytic activity of the electroless plating catalyst. For example, when the electroless plating film is formed on only a portion of the surface of the substrate, the hyperbranched polymer solution is applied to the portion where the electroless plating film is not formed to form the hyperbranched polymer layer. Thereafter, by bringing the electroless plating catalyst solution and the electroless plating solution into contact with the substrate on which the hyperbranched polymer layer is formed, the electroless plating film can be formed only in the portion where the hyperbranched polymer layer is not formed. The reason for this is not certain, but it is speculated as follows. The hyperbranched polymer on the substrate firmly traps the electroless plating catalyst (Pd or the like) in the electroless plating catalyst solution in the state of metal ions. For this reason, metal ions cannot be reduced to become a metal having an oxidation number of 0 (zero). Since the Pd ion does not exhibit electroless catalytic activity, it is presumed that an electroless plating film is not formed on the hyperbranched polymer layer. In addition, this mechanism is only estimation, and this embodiment is not limited to this.

Example

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited by the following Examples and Comparative Examples.

[Example 1]

<Synthesis of Polymer A1>

A group having an amide group was introduced into a commercially available hyperbranched polymer (polymer D) represented by formula (6) to synthesize polymer A1 represented by formula (5). Polymer A1 represented by Formula (5) is a polymer represented by Formula (1), In Formula (1), A ¹ is group represented by Formula (2); A2 is group represented by Formula ( ³ ), R< ¹ > is a single bond, R< ² > is hydrogen, R< ³ > is an isopropyl group; A ³ is a dithiocarbamate group represented by Formula (4), R ⁴ and R ⁵ are ethyl groups, and R ⁰ is a vinyl group or an ethyl group.

First, a hyperbranched polymer (polymer D) represented by formula (6) (Nissan Chemicals Co., Ltd., Hypertech HPS-200) (1.3 g, dithiocarbamate group: 4.9 mmol), N-isopropylacrylamide (NIPAM) (1.10 g, 9.8 mmol), α,α' azobisisobutyronitrile (AIBN) (81 mg, 0.49 mmol), dehydrated tetrahydrofuran (THF) (10 mL) were added to a Schlenk tube, freeze degassed was performed 3 times. Thereafter, the reaction was stirred overnight (18 hours) at 70°C using an oil bath, and after completion of the reaction, the mixture was cooled with ice water and appropriately diluted with THF. Then, it was reprecipitated in hexane, and the obtained solid was vacuum-dried at 60 degreeC overnight. The dried solid was further dissolved in THF and reprecipitated with water. The obtained solid was vacuum-dried at 60 degreeC overnight, and the product was obtained. The yield of the product was 69%.

¹ H-NMR (nuclear magnetic resonance) measurement and IR (infrared absorption spectrum) measurement of the product were performed. As a result, it was confirmed that the amide group was introduced into the commercially available hyperbranched polymer (polymer D) represented by the formula (6), and the polymer A1 represented by the formula (5) was produced. In the IR spectrum of the polymer A1 shown in Fig. 2, absorption a1 derived from the amide group (around 1600 to 1700 cm ^-1 ) appeared. In addition, based on the Peak1 (4.0 ppm) and Peak2 (3.7 ppm) of the ¹ H-NMR spectrum of the polymer A1 shown in Fig. 3, by the following formula, the number of moles of the sulfur-containing group A ³ in A ² The ratio (molar ratio: N/S) of the total number of moles of the amide groups included was calculated. The molar ratio (N/S) was 0.96.

(N/S)=(I _P1 -I _P2 )/(I _P2 /2)

I _P1 : Peak area of Peak1

I _P2 : Peak area of Peak2

3, the schematic diagram of the structure of polymer A1 is shown together. Peak1 is a peak derived from one hydrogen (c) of two hydrogens (b) of the sulfur-containing group (A ³ ) and one hydrogen (c) of the amide group (A ² ) in the terminal group of the polymer A1, , Peak2 is a peak derived from two hydrogens (a) among sulfur-containing groups (A ³ ).

Then, the molecular weight of the product was determined by GPC (gel permeation chromatography). The molecular weight was number average molecular weight (Mn) = 9,946 and weight average molecular weight (Mw) = 24,792, and the number average molecular weight (Mn) and weight average molecular weight (Mw) unique to the hyperbranched structure were significantly different values.

Polymer A1

polymer D

[Example 2]

<Synthesis of Polymer A2>

Polymer A2 was synthesized in the same manner as in Example 1 except that NIPAM was 2.20 g and the reaction time was 24 hours. In the same manner as in Example 1, ¹ H-NMR measurement, IR measurement, and molecular weight measurement of the product (polymer A2) were performed. As a result, it was confirmed that polymer A2 was a hyperbranched polymer represented by Formula (5) similarly to polymer A1. In addition, the molar ratio (N/S) was 1.22, number average molecular weight (Mn) = 10,700, and weight average molecular weight (Mw) = 25,200.

[Example 3]

<Synthesis of Polymer A3>

Polymer A3 was synthesized in the same manner as in Example 1 except that the reaction time was 8 hours. In the same manner as in Example 1, ¹ H-NMR measurement, IR measurement, and molecular weight measurement of the product (polymer A3) were performed. As a result, it was confirmed that polymer A3 was a hyperbranched polymer represented by Formula (5) similarly to polymer A1. In addition, the molar ratio (N/S) was 0.78, number average molecular weight (Mn) = 9,400, and weight average molecular weight (Mw) = 24,000.

[evaluation]

Polymers A1 to A3 synthesized in Example 1 were evaluated below.

(1) Evaluation of solubility

Polymers A1 to A3 were added to each of the four solvents shown in Table 1 so that the concentration was 2% by weight, and whether or not to be dissolved was tested. The test was conducted at room temperature. A result is shown in Table 1.

Polymers A1 to A3 were dissolved in general-purpose solvents such as tetrahydrofuran (THF), methyl ethyl ketone (MEK), cyclohexanone, and toluene.

(2) Evaluation of metal trapping ability 1

To the substrate on which the hyperbranched polymer layer was formed, an electroless plating catalyst (Pd) was applied and an electroless plating treatment was performed, and the metal trapping ability of the hyperbranched polymer was evaluated. When the metal trapping ability is high, since the hyperbranched polymer strongly adsorbs (traps) many electroless plating catalysts, the electroless plating reaction hardly occurs. On the other hand, when the metal trapping ability is low, the number of electroless plating catalysts adsorbed by the hyperbranched polymer is small, and since the adsorption is not strong, the electroless plating reaction tends to occur. As such, the plating reactivity on the hyperbranched polymer layer is determined by the metal trapping ability of the hyperbranched polymer. In this evaluation, the hyperbranched polymer was used as the catalyst activity inhibitor, and the polymer having a high effect of the catalyst activity inhibitor was evaluated as having a high metal trapping ability. This evaluation performed the same evaluation also about the polymer D in addition to the polymers A1 - A3 for comparison.

<Evaluation method>

Polymer A1 was dissolved in toluene to prepare a polymer solution having a polymer concentration of 0.5 wt%. A solution of polymer A1 was dip-coated on a resin substrate (polyamide, manufactured by Toyobo, Viroamide) and dried to form a polymer layer of polymer A1. By the same method, polymer layers of the polymers A2, A3 and D were formed on the resin substrate using the polymers A2, A3 and D.

Next, the electroless-plating catalyst was provided to the resin base material in which the polymer layer was formed by the following method using a commercially available catalyst liquid for electroless-plating. First, the resin substrate was immersed in a sensitivity imparting agent (Okuno Pharmaceutical Co., Ltd., Sensitizer) at room temperature and subjected to a sensitizer treatment by irradiating ultrasonic waves for 5 minutes to adsorb the tin colloid onto the surface of the resin substrate. Thereafter, the resin substrate was taken out with the sensitizer and sufficiently washed with water. Next, the resin substrate was immersed in a catalytic treatment agent (manufactured by Okuno Pharmaceutical Co., Ltd., Activator) at room temperature, and left to stand for 2 minutes to perform an activator treatment, whereby Pd was adsorbed on the surface of the resin substrate. Thereafter, the resin substrate was taken out from the catalytic treatment agent and thoroughly washed with water.

The resin base material to which the electroless plating catalyst was provided was immersed in 61 degreeC electroless copper plating solution (Okuno Pharmaceutical Co., Ltd. make, OPC-NCA) for 15 minutes, and the presence or absence of generation|occurrence|production of the electroless plating film|membrane was judged.

The metal trapping ability of polymers A1 to A3 and D was evaluated according to the following evaluation criteria. Table 2 shows the evaluation results.

<Evaluation criteria for metal capture ability>

(circle): An electroless plating film was not produced|generated. Therefore, the metal trapping ability is high.

x: An electroless plating film was produced|generated. Therefore, the metal trapping ability is low.

As shown in Table 2, polymers A1-A3 had high metal capture|acquisition ability. On the other hand, the polymer D ((N/S)=0) which did not contain an amide group in the terminal group had low metal capture|acquisition ability. The reason for this is presumed to be that the polymer D cannot trap a metal since it does not have an amide group interacting with the metal at the terminal group.

(3) Evaluation of metal trapping ability 2

The base material on which the hyperbranched polymer layer was formed was immersed in the liquid in which the metal was dissolved, the metal was recovered, and the metal trapping ability of the hyperbranched polymer was evaluated. That is, in this evaluation, a hyperbranched polymer was used as a metal recovery agent.

<Evaluation method>

First, as a liquid in which a metal is dissolved, the following three types of solutions were prepared. The metal concentration in each solution is 150 ppm.

Pd solution: Commercially available Pd aqueous solution (Okuno Pharmaceutical Co., Ltd., Activator)

Pt solution: aqueous potassium tetrachloroplatinum(II) acid solution

Ag solution: aqueous silver nitrate solution

By the method similar to evaluation 1 of (2) metal capture|acquisition ability mentioned above, the resin base material which has a polymer layer was manufactured using polymer A1. Moreover, for comparison, the resin base material which does not have a polymer layer was also prepared. The resin base material with a polymer layer and the resin base material without a polymer layer were respectively immersed in Pd solution for 5 minutes, and water washing and drying were performed. Similarly, the resin substrate having a polymer layer and the resin substrate having no polymer layer were immersed in the Pt solution and the Ag solution, respectively, and washed with water and dried.

The surface of the resin substrate immersed in each solution was subjected to XPS analysis (X-ray photoelectron spectroscopy). In the resin substrate immersed in the Pd solution, Pd was quantified, in the resin substrate immersed in the Pt solution, Pt was quantified, and in the resin substrate immersed in the Ag solution, Ag was quantified. A result is shown in Table 3.

As shown in Table 3, in all of Pd, Pt, and Ag, the resin base material which has a polymer layer was able to collect|recover many metals. From this result, it has been confirmed that the polymer A1 has the ability to trap metals Pd, Pt, and Ag.

The novel hyperbranched polymer of the present invention has a metal trapping ability. For this reason, for example, it can be utilized as a metal recovery agent which collect|recovers the said metal in the liquid in which the metal is melt|dissolved, and a catalytic activity inhibitor which interferes with the catalytic activity of an electroless plating catalyst.

Claims (13)

It is represented by following formula (1), and a weight average molecular weight is 1,000-1,000,000, The hyperbranched polymer characterized by the above-mentioned.
[Formula 1]

In formula (1),
A ¹ is a group containing an aromatic ring,
A ² is a group containing an amide group,
A ³ is a group containing sulfur,
R ⁰ is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms,
m1 is 0.5-11, n1 is 5-100. The method of claim 1,
In the formula (1),
A ¹ is a group represented by the following formula (2),
A ³ is a dithiocarbamate group, hyperbranched polymer, characterized in that.
[Formula 2]

3. The method of claim 1 or 2,
In the formula (1),
A2 is group represented by following formula ( ³ ), The hyperbranched polymer characterized by the above-mentioned.
[Formula 3]

In formula (3),
R ¹ is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, or a single bond,
R ² and R ³ are each a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or hydrogen. 4. The method of claim 3,
In the formula (3), R ¹ is a single bond, R ² is hydrogen, R ³ is a hyperbranched polymer, characterized in that the isopropyl group. 5. The method according to any one of claims 1 to 4,
In the formula (1),
A ³ is group represented by following formula (4), The hyperbranched polymer characterized by the above-mentioned.
[Formula 4]

In formula (4),
Each of R ⁴ and R ⁵ is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or hydrogen. 6. The method of claim 5,
In the formula (4), R ⁴ and R ⁵ is an ethyl group, characterized in that the hyperbranched polymer. 7. The method according to any one of claims 1 to 6,
In formula (1),
A hyperbranched polymer characterized in that the ratio of the total number of moles of the amide groups contained in A ² to the number of moles of the sulfur-containing group A ³ is 0.5 or more and less than 1.5. 7. The method according to any one of claims 1 to 6,
In formula (1),
A ³ is a dithiocarbamate group,
The hyperbranched polymer, characterized in that the ratio of the total number of moles of the amide group contained in A ² to the number of moles of the sulfur-containing group A ³ is 0.5 to 1.5. 9. The method according to any one of claims 1 to 8,
In Formula (1), R ⁰ is a vinyl group, The hyperbranched polymer characterized in that it. 9. The method according to any one of claims 1 to 8,
The hyperbranched polymer is a hyperbranched polymer, characterized in that the hyperbranched polymer in the formula (1), wherein R ⁰ is a vinyl group, and R ⁰ is a mixture of a hyperbranched polymer having an ethyl group. A metal recovery agent for recovering the metal in a liquid in which the metal is dissolved, the metal recovery agent comprising the hyperbranched polymer according to any one of claims 1 to 10. A metal recovery method for recovering the metal in a liquid in which the metal is dissolved,
Dissolving the hyperbranched polymer according to any one of claims 1 to 10 in a solvent to prepare a hyperbranched polymer solution;
forming a hyperbranched polymer layer by applying the hyperbranched polymer solution on a substrate;
and contacting the liquid with the hyperbranched polymer layer to adsorb and recover the metal in the liquid. 11. A catalyst activity inhibitor for hindering the catalytic activity of an electroless plating catalyst, comprising the hyperbranched polymer according to any one of claims 1 to 10.

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